1:2 homogeneous cobalt complexes of phenyl-azo-phenol,phenyl-azo-naphthol or phenyl-azo pyrazolone dyes having bound to the phenyl nucleus an anilino or naphthylamino substitutent



United States Patent US. Cl. 260-147 8 Claims ABSTRACT OF THE DISCLOSURE1:2 homogeneous cobalt complexes of phenyl-azophenyl and phenyl-azonaphthyl dyes, having bound at the ortho position to one phenyl nucleuseither an anilino or a naphthylamino substituent, are useful for dyeingwool, silk, leather, polyamide fibers and natural and regeneratedcellulose fibers with good fastness to light, washing, perspiration, gasfumes, acids, alkalis, water, sea water, carbonising, bleaching,milling, rubbing, pressing, stoving and cross dyeing.

This invention relates to cobalt complex dyes of the azo series. In themetal-free state these dyes have the formula:

In this formula:

R represents a hydrocarbon radical which may be substituted,

R the radical of a coupling component, and

X a group which is metallisable in the adjacent position to the azogroup. The ring A may contain further substituents if desired.

Dyes especially preferred are those which, unmetallised, have theformula:

D (II) or the formula:

B '1IIH N=NF("JOH Hi N vv (III) In Formulae II and III the rings A, Band D may be substituted or unsubstituted. All the rings may bear, inaddition, non-water-solubilising substituents, for example alkyl oralkoxy groups, halogen atoms, carboxylic acid ester, acylamino, nitro,cyano, hydroxyl or amino groups. W denotes a hydrogen atom or asubstituted or unsubstituted hydrocarbon radical and Z the hydroxylgroup or an amino group. When W stands for aryl, it is preferable for atleast one of the rings A and W to be substituted by a Water-solubilisinggroup, for example a sulphonic acid, carboxylic acid, sulphonamide,carbonamide or an organic sulphonyl group.

The rings A, B and D contain preferably sulphonic acid, carboxylic acid,sulphonic acid amide or carboxylic acid amide groups, monoordi-substituted sulphonic acid amide groups or carboxylic acid amidegroups; for eX- ample, a sulphonic acid amide or carboxylic acid amidegroup substituted by one or two methyl, ethyl or hydroxyethyl groups orby a phenyl radical which also may be substituted; alkylsulphonyl groupswith, for example, 1 to 4 or more particularly 1 to 2 carbon atoms;arylsulphonyl groups, notably substituted or unsubstitutedphenylsulphonyl groups; alkyl or alkoxy groups having 1 to 5 carbonatoms, e.g. methyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl,n-amyl, isoamyl, methoxy, ethoxy or n-butoxy; halogen atoms, such aschlorine, bromine or fluorine atoms; nitro or hydroxy groups; free aminogroups or substituted amino groups, e.g. acylamino groups such as loweralkanoylamino groups, lower alkylamino groups or arylamino groups, e.g.phenylamino or alkylphenylamino groups.

A process for the production of dyes of Formula I consists indiazotising an amino of formula:

N-Ra

where R represents an acyl group, and coupling with a compound offormula:

alkyl radical, e.g. methyl, ethyl, butyl, Z-hydroxyethyl,

Z-methoxyethyl, Z-ethoxyethyl, 3-methoxybutyl, a substituted orunsubstituted aralkyl or cycloalkyl radical, e.g. benzyl, phenylethyl,cyclohexyl, 4-methylcyclohexyl, or preferably a mononuclear, substitutedor unsubstituted 0 aryl radical, e.g. phenyl, methylphenyl,dimethylphenyl,

ethylphenyl, chlorophenyl, bromophenyl, fluorphenyl, methoxyphenyl,ethoxyphenyl or nitrophenyl. R may also be a substituted orunsubstituted naphthyl radical.

Examples of suitable coupling components of formula V are aromatichydroxy compounds, such as 4-methyl-1- hydroxybenzene,1,3-dihydroxybenzene, 2-hydroxynaphthalene,1-hydroxy-4-methoxynaphthalene, 1-hydroxy-5,8- dichloronaphthalene,2-hydroxy-8-acetylaminoor -8- methylsulphonylaminonaphthalene, 1hydroxynaphthalene-4- or -5-sulphonic acid, 2-hydroxynaphthalene-4-, -6-or -7-sulphonic acid or -6- or -7-sulphonic acid amide, 1 hydroxy-6- or-7-amino, methylamino-, phenylamino, (4 methoxyphenylamino)-, -(2',4',6'trimethylphenylamino) naphthalene 3 sulphonic acid, 1- hydroxy 8acetylaminonaphthalene 3,6 or 3,5 disulphonic acid amide; aromaticcompounds having a primary or secondary amino group, such as1,3-diaminobenzene, 1-aminonaphthalene-4-sulphonic acid, 2-amino-, 2-phenylamino-l or 2-methylamino-5-hydroxynaphthalene- 7-su1phonic acid,2-amino-, 2-phenylamino-, 2-(2', 4, 6- trimethylphenylamino)- or2-methylamino 8 hydroxynaphthalene-6-sulphonic acid; 5- pyrazolones orS-aminopyrazoles, such as 1-phenyl-3-methyl-5-pyrazolone or its -3'- or-4'-sulphonic acids; 1-(2, 5-dichlorophenyl)- or1-(2-chloro-6'-methylphenyl)-3- methyl 5 pyrazolone- 4'-sulphonicacid,1-(2-chlorophenyl)-3-methyl 5 pyraZlone-5'-su1phonic acid,1-(3'-aminosulphonylphenyl)-3- methyl--pyrazolone,1-phenyl-3-methyl'5-aminapyrazole or its -3'- or -4'-sulphonic acids or-3'-sulphonic acid amide; acylacetyl derivatives, such asacetoacetylaminobenzene or its -3- or -4-sulphonic acids,l-acetoacetylaminonaphthalene 4 or 5- sulphonic acid, 2acetoacetylaminonaphthalene-5-, -6- or -7-sulphonic acid, 1-acetoacetylamino-2-ethylhexane, 1 acetoacetylambinobutame; andbarbituric acid.

The starting amines of Formula (IV) can be produced in accordance withthe particulars given in the Journal of the American Chemical Society75, p. 6336, 1953.

The amine of Formula IV is best diazotised in the temperature range of 0to 10 C., or preferably 0-5 C. The coupling reaction can be convenientlycarried out at 0 to 60 C. in acid, neutral or alkaline medium, e.g. at0-20 C. in a weakly acid, neutral or alkaline medium when thesubstituent X is an enolic or phenolic hydroxyl group, and at -60" C. inacid medium when the substituent X is an unsubstituted ofmonosubstituted amino group.

The acyl group can be split ed by heating the azo dye in the presence ofa dilute mineral acid, e.g. 2-10% hydrochloric acid or sulphuric acid,at 70120 C. or, preferably, 90-100 C., and if necessary under pressure,or in the presence of a solution of an alkali metal hydroxide, e.g.2-15% sodium or potassium hydroxide solution, at 70l20 C. For thispurpose an aqueous, aqueous-organic or organic medium can be used, e.g.an aqueous medium when the dye contains water-solubilising groups, suchas SO H, or in the case of alkaline 'hydrolysis, COOH or --SO NH or inaqueous-organic or organic medium when the dye is virtually insoluble orsparingly soluble in water. Examples of suitable organic solvents arealcohols, such as methanol, ethanol, isopropanol, n-propanol,2-methoxyor Z-ethoxy-ethanol, 2-(2-ethoxy)ethoxyethanol; ethers, such asdioxan; or, in the case of acid hydrolysis, carboxylic acids, e.g.acetic or propionic acid.

When the substitutent R is an alkylsulphonyl or arylsulphonyl group,hydrolysis is effected to best advantage in a concentrated mineral acid,e.g. in boiling -35% hydrochloric acid or boiling 400-50%- hydrobromicacid, or in about 70-85% sulphuric acid at 100-150.

After cleavage of the radical R the metallisable azo dyes, if preferredafter neutralisation of the hydrolysing solution, are precipitated bydilution with water or by the addition of salt filtered ofi and dried.

The dyes of Formula I can be produced yet more advantageously bydiazotising an amine of formula:

Halogen where halogen represents preferably chlorine or bromine,coupling with a compound of formula:

| H-Rz (VI and condensing the resulting azo compound with an amine offormula:

NH: (VIII) The condensation reaction can be perfomed very expedientlywith the addition of metals or metal salts, especially copper salts, andof basic condensing agents if required, e.g. sodium carbonate. In thiscase the copper complexes of the dyes of Formula I are obtained, whichcan be readily demetallised by treatment with acids, e.g. sulphuricacid, and subsequently converted into the cobalt complexes.

The final dyes obtained can be applied to wool, polyamide fibres,cotton, regenerated cellulose fibers and other suitable textile fibersby exhaustion dyeing methods, and the dyeings subsequently metallised bytreatment with cobalt compounds. Alternatively, the dyes can bemetallised in substance, e.g. in aqueous solution or an organic medium,such as formamide or in a concentrated aqueous solution of an alkalimetal salt of a lower aliphatic monocarboxylic acid. It is of advantageto allow an amount of a cobalt-yielding agent containing less than twobut at least one atom of cobalt to act upon two molecules of the monoazodye. Examples of suitable cobalt compounds are cobaltous formate,cobaltous acetate and cobaltous sulphate. When the metallising reactionis carried out in the concentrated aqueous solution of an alkali metalsalt of a lower aliphatic monocarboxylic acid, water-insoluble cobaltcompounds such as cobalt hydroxide or cobalt carbonate can be used.

It is of special advantage to carry out metallisation in an aqueous oralkaline medium, to which the metal compounds are added in the presenceof compounds which maintain the metals dissolved in complex combinationin caustic-alkaline medium, e.g. tartaric, citric or lactic acid.

The resulting cobalt complex compounds, if desired after the addition ofthe organic metallising solution to water, are precipitated from aqueousmedium by the addition of salt, filtered off, washed if necessary anddried.

The cobalt-containing azo dyes thus obtained are homogeneous metalcomplex compounds in which essentially one atom of cobalt is bound totwo molecules of the monoazo compound, i.e. 1:2 complexes in which onemolecule of monoazo compound is bound to approximately 0.3 to 0.7 atomsof metal.

These cobalt-containing azo dyes dye wool, silk, leather and polyamidefibres from a neutral or acid dyebath, and natural and regeneratedcellulosic fibres from a neutral or alkaline dyebath. Those which aresufiiciently soluble in organic solvents can be used for the spin dyeingof fibreforrning materials in solution in organic solvents and for thepigmentation of surface coatings and plastics. The dyeings and coatingsthus produced have good fastness to light, washing, perspiration, gasfumes, acids, alkalis, water, sea water, carbonising, bleaching,milling, rubbing, pressing, stoving and cross dyeing.

In the following examples the parts and percentages are by weight andthe temperatures in degrees centigrade.

EXAMPLE 1 22.6 parts of 2-amino-N-acetyl-1,1'-diphenylamine aredissolved in 1000 parts of water and 35 parts of 30% hydrochloric acid.The solution is cooled to 05 C. and a solution of 6.9 parts of sodiumnitrite in 20 parts of water is added with stirring. The pale yellowdiazo solution thus formed is dropped into a solution of 25.3 parts of1-(3'- aminosulphonylphenyl)-3-methyl-5 pyrazolone in 200 parts of waterand 13.5 parts of 30% sodium hydroxide 5 which are added 20 parts ofpotassium hydroxide. The solution is maintained at the boil for 12hours, during which it turns yellow-brown in colour. Subsequently it isdiluted with 200 parts of water and acidified with concentratedhydrochloric acid until it reacts acids to Congo Red paper. Theprecipitated brown dye is suctioned ofi, washed with water and dried.

9 parts of this dye are dissolved with 3 parts of cobalt sulphateheptahydrate in 115 parts of formamide. The solution is held for 1 hourat 120 and then diluted with 10 parts of water. The cobalt-containingdye settles out and is suctioned off, washed with water and stirred into90 parts of 10% sodium hydroxide solution with heating. When everythinghas dissolved it is salted out with 18 parts of sodium chloride,suctioned off, washed with 20% sodium chloride solution, dried andground. It is obtained as a dark powder which dissolves in water to givegrey solution and dyes wool, silk and polyamide fibres in fast greyshades.

EXAMPLE 2 30.4 parts of2-amino-N-acetyl-methylsulphonyl-1,1'-diphenylamine are dissolved in 50parts of methanol. 30 parts of 30% hydrochloric acid and 500 parts ofwaten are added to the solution, after which it is diazotised at with6.9 parts of sodium nitrite. The pale yellow diazo solution is adjustedto pH 4 with sodium acetate, on which an alkaline solution of 14.4 partsof 2-hydroxynaphthalene is slowly added so that the pH of the couplingsolution is from 4 to 5. The temperature is about 0 to The dye settlesout with an orange-red colour and when the coupling reaction is completeit is suctioned off, washed and dried.

24 parts of the dry dye are dissolved in 300 parts of methanol, andafter the addition of 8 parts of potassium hydroxide the solution isstirred for 4 hours at the boil with reflux until the acetyl group issplit off. The wine-red dye solution is run into water and theprecipitated dye filtered oif and washed. 14 parts of the dye aredissolved in 280 parts of dimethyl formamide and 4.7 parts of cobaltsulphate hept'ahydrate. The solution is held at 120 for 1 hour, then1000 parts of 5% hydrochloric acid are added, causing the 1:2 metalcomplex dye to precipitate. It is suctioned off and washed with water.The still moist dye paste is stirred in a 5% sodium hydroxide solutionfor 2 hours, suctioned off and dried. It is obtained as a dark bluepowder which goes into solution in organic solvents and water with ablue coloration and dyes wool, silk and polyamide fibres in fast navyblue shades. The Z-amino-N- acetyl-4-methylsuphonyl-1,1'-diphenylaminecan be produced as follows: 536 parts of2-nitro-4-methylsulphonyll,1'-diphenylamine in 1700 parts of aceticanhydride are 5 heated to the boil, on which 50 parts of freshly meltedzinc chloride are carefully added. Boiling is continued for 1 hour withreflux. The reaction product is run in a thin jet into 5000 parts ofwater at with stirring, which is continued until the mixture has cooledto room temperature. The product settles out and is suctioned oil anddried. 33.4 parts of2-nitro-N-acetyl-4-methylsulphonyl-l,1'-diphenylamine are dissolved in50:50 Water: ethanol solution. 10 parts of Raney nickel are added andhydration carried out with hydrogen at 40 and normal pressure. Oncomplete reduction of the nitro group the alcoholic solution isevaporated to dryness. The amino compound thus formed is suitable forthe production of azo dyes.

Dyeing example 1 part of the cobalt-containing dye disclosed in Example2 is dissolved in 6000 parts of water of 40 with the addition of 3 partsof ammonium sulphate. parts of wool are entered into this dyebath, whichis then raised to 100 in about 30 minutes. The wool is dyed for 1 hourat the boil, the water lost by evaporation being replaced from time totime and is subsequently removed, rinsed with water and dried. It isdyed in a level navy shade with very good fastness to washing andmilling and good light fastness. Nylon and other polyamide fibres can bedyed by the same method.

The following table contains particulars of further dyes which areobtainable in accordance with the present invention. In the metal-freestate they have the formula:

X I Example No. R1 -R2 Y Shade 2 Phegyl 2-hydroxynaphthyl-1 H Grey C2H5CHzCH2OH 12 -CHz-CHz-O CH3. fin a s 2 1 -I irT- 5 o1 D0:

CH3(5)-C1 13 -CHz-CHz-CH2O can an (3)--S OzN D0.

OH /CHa 1i C 7 (5)S Oz-N D0.

ozmon 15 CH -N0z Same as above (4)S O2NH\ Do.

X Example N0. R1 -I i2 n Shade I 16 -CH1 3 H a Blue-grey.

$0203, Ct] 17 0H2- 3 Q0 1s 3 s 0 (9-0021; Blue.

19 Same as above (5)NO2 Do.

20 -CH: -.-.-do 5 c1 Do.

21 0 .....do (4)Br Do.

22 s 02- (3)-F-(5)--O1 Do.

CH2 23 Same as above (5)OH Do.-

24 OCH; 1103s (9-0211, Do.

25 -C c1 Same as above (5)GOOCH; Grey.

26 -----do (4)C0NHC H Do.

OH 27 Q m H Blue.

(50011 S O H 2s 0 -01: H Do;

29 HOaS- -OH H Do.

NHCOCH;

NHCH;

30 C S 0 OH H Do.

(IJONHCHQ x Example No. R1 R2 Y Shade 31 -s 020E; OH H Blue.

32 Q-s OzNHz OH H Do;

(502m NH s 03H cmoonn OH 34 Br H Do.

H NO S s OzNH OH 35 M M H 36 (4)S OzCHa Brown.

I NHCO CzHs OH on 31 O0 0H3 OOH 4 -s 020m Do.

I as CH3 0H (5)-s 020113 Do.

39 0 (5)s 02cm Blue;

| OCHa 2 's 40 -43 Mm 41 Q NHCOOH: (s)s 01cm Brown.

42 Q (5)-s 020m D0- Shade Example No.

CHaCONH 0 Ha-S O 2-N H fin SOzH

mn-mswon H.....--...--.--......-.-------- Blue.-

I Example No. R1 -R2 Y Shade 54 G H Blue.

CH3NH-OzS 0H 55.. fin I OH (5)SO CH Do.

56 do I OH H Do 57 dn OH H Do.

ONE S0;H

53 An (I)H H Do.

so,H

59 do CH O-O-NH S0311 H Do:

Do. SO H CH3 0H 61 an MPG-NH H Do.

JJH, 50,11

CHaC ONH O H HOaS- SO3H CHzCONH OH 63 fin HzN-OzSQSOzNH: H D0 CH C ON HOH @SOIH 64.. fin l H Do.

Example N 0. R1 R2 Y1, Shade 65 Q -soZNH2 H Blue SOzNHz F 66 do H Do.

67 do NHZ (5)SO;GH3 Brown.

as .-do SO3H [I)NHz H Blue;

| "1 k OH A 71-. do NH; (5) SOQCHQ Do.

SOaH

72 do Nl i Same as above Do;

OH H O CH I 73.. (in NH H Do.

SOaH- Example No.

rln

- NHCHI SOzNHg H OH (5)SOaCH 03 Same as above.

( SO-,CH|

Shade H Blue;

...... Olive.-

X I Example No. R: R2 Ya Shade 84 --O NH: (5) 302GB; Olive.

I- 3 V (In,

85 ..do NH: H D0.

I SOzNH:

86 .-do NH: H Do.

v-Q l N R7 NH: H D0.

-Ii1' -SO:NH I N l CH3 88 (5)S0:CH3 Do.

NHCO-(iH-O 0 CH3 3g fin H Do.

NH-C O-(lJ HCOCH3 S O H 90 H Do.

SOaH- NH-C O-C|3HC O-CH;

NH-C O-(EH-C O-CH m a m 0- NH-C 0-?H-C 0-011: 02 fin (n H Do.

I S 03H NH-C O(|3HC 0-011: 93 M in H I S ONE:

I'VE-C O|CHC O-GHa 94 .-.do H Do.

I S 01H 0 do H Q. Do.

NH-C O-(EH-CO-CH:

Example N 0. R1 R2 Yn Shade 96 -C soan NH-o -(|JHC0-CHa H Olive 97 doCHg-C O--(|JHC ONH-C III-H (4) S OzCHa D0.

98" do CH;0O(l3HO o-NH-C4H9 5 -s 02cm Blue.

99 OCH: H Same as above Do.

100 0001B; Same as above E fin a'. -6 an a.

(iCHa 102 0 do D0.

103 0 do do Do:

104 Q do an Do.

106 d0 do Do.

rln (3)CH (5)S 0 H Navy blue.

EXAMPLE 108 20.5 parts of l-amino-2-chloro-5-methylsulphonylbenzene arediazotised with 6.9 parts of sodium nitrite and parts of 30%hydrochloric acid, and the diazo compound coupled in acetic acidsolution with 14.4 parts of 2-hydroxynaphthalene. The resultingorange-red azo compound is filtered off, washed and dried. 36 parts ofit are dissolved in 150 parts of dimethyl formamide, with the subsequentaddition of 5 parts of copper sulphate crystals, 15 parts of1-amino-4-ethoxybenzene and 10 parts of anhydrous sodium carbonate. Thereaction solution is raised to 100 and maintained at this temperaturefor 2 hours. It is then adjusted acid to Congo paper with 2-normalsulphuric acid and boiled for a further 2 hours with reflux. The dyesettles out and is filtered 01f, washed and dried. It is free fromcopper 23 2'4 Formulae of representative dyes of the foregoing exam-Having thus disclosed the invention what We claim is: ples are asfollows: 1. A homogeneous 1:2-cobalt complex of a monoazo Example 2.The1:2-cobalt complex compound of dye of the formula:

the azo dye of the formula:

NH HO wherein:

A is a member selected from the group consisting of hydrogen and ethoxy;

A is para to either the amino or the azo group and is a member selectedfrom the group consisting of hydrogen Q OH and methylsulfonyl; and

I I A is a member selected from the group consisting of2-hydroxynaphthyl 1,6-aminosulfonyl-2-hydroxynaphthyl 1,2hydroxy-8-methylcarbonylaminonaphthyl-1,

2 hydroxy 8methylcarbonylaminonaphthyl-1,2-hydroxy-5-methyl-3-methy1carbonylaminophenyl,5020113 6 l-hydroxy 4 methoxynaphthyl-Z and 3-methyl-1-phenyl-5-pyrazolonyl-4. 2. The complex according to claim 1 of the dyeof the SOzOH;

Example 41.The 1:2-cobalt complex compound of the azo dye of theformula:

Example 43.The 1:2-cobalt complex compound of the azo dye of theformula: formula:

OHaSOzQ-N-H HO SO2CH3 JH; 35

N=N- Example 45.The 1:2-cobalt complex compound of the azo dye of theformula:

3. The complex according to claim 1 of the dye of the O OR formula:

NH- I l N=N SOzCH; oo-cn;

Example 53.-The 1:2-cobalt complex compound of the azo dye of theformula: 802GB;

4. The complex according to claim 1 of the dye of the 1 formula:

Q OH

I N=N NHc0oH, Boa-NH:

Example 75.The 1:2-cobalt complex compound of the azo dye of theformula: SOzOH: CHa

5. The complex according to claim 1 of the dye of the NH formula:

N SOZCH;

I SOzCH; (BCH;

25 26 6. The complex according to claim 1 of the dye of the 8. Thecomplex according to claim 1 of the dye of the formula: formula:

503013 O-CHa 15 References Cited 7. The complex according to claim 1 ofthe dye of the UNITED STATES PATENTS formula: 2,529,444 11/1950Bestehorn et a1 260149 2,824,094 2/1958 Ackermann et a1. 260-146 202,839,520 6/1958 Neier 260-149 X 3,040,019 6/1962 Neier 260151 X 0-1 on3,169,123 2/1965 Neier 260151 X =N- FLOYD DALE HIGEL, Primary Examiner25 US. Cl. X.R.

842, 43; 260-149, 151, 162, 193, 197, 199, 200, 201, SOz-NHz 202 UNITEDSTATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,514,43 Datedlay 26 1970 Inv nt fl I-YAL'IEP. (113mm and IIJ'IITJZ VICKI It iscertified that error appears in the above-identified patent and thatsaid Letters Patent are hereby corrected as shown below:

Column 1, line 60, in the formula, n should read 3 Column 2, line 27,"amino" should read amine. Column 3, line 1, "amino,' should readamlno,-; line 7, "Mxeovlamino-l" should read phenylaminoline 14,"sulnl'zonicacid" should read sulohonic acid-; line 16, "amimwvrazole'should read amrlnonvrazole--; line 45, "C OU" should read --COOH-; line56, "400" should read 40; line 61 "salt" should read salt,; line 7, inthe formula, should read I! I 2 NH 2 Column 5, line 29, "1 should readlO Column 6, line 3, "methyl.- sunhonvl" should read -methvlsulnhony]Column 15, in the formula of Examnle I30. 69, should read in the S0 H SI formula of Example No. 72, should read in the formula of Example No.73, y" should read Column 17, in the formula of lixamnle No. 77, 11should read ()H in the formula of Example 310. 78, "OH should read FORMPC4050 H0459) USCOMM-DC 60376-969 Q U 5. GOVERNMENT PRINTING OFFICE il!O36-33l Patent No. 3, Dated aw 26, 1970 Inventor(s) WALTEP IJEHRLI andWIT-17 wlcm PAGE 2 It is certified that error appears in theabove-identified patent and that said Letters Patent are herebycorrected as shown below:

---O1I Column 18, Example 75, should read (A)-. Column 19,

in the formula of Examnle Q4, II!Cfi(TICfi-CI should read YR I -Y -IIHCTH-C C Column 2.1, line 35, in the formula,

should read Column 24, line 1", "1,6" should read 1, 6-;

a line 2' "1,2" should rear -l, 2; line 21, delete"2-hydroxv-8-methylcar hon laminonanhthvl].,

Signed and sealed this 10th day of November 1970.

(SEAL) Attest:

EDWARD M.FLETCHER,JR. WILLIAM E. SCHUYLER, JR. Attesting OfficerCommissioner of Patents FORM PO-IOSO (ID-69] USCOMNPDC O37 p9 0 u s.uovnuuzur murmur. ornc: In! o-Jn-Ju

